Process for producing catalyzers for hydrogenation



B. W. ELDER.

PROCESS FOR PRODUCING CATALYZERS FOR HYDROGENATION.

' APPLICATION FILED JUNE 7, 19I8.

1,331,904.. Patented Feb. 24, 1920.

' catalytichydrogenati-on ofoils and or other unsaturated substances.

UNITED STATES PATENT OFFICE.-

-13IEITJTAIINIIIQ'NV. ELDER, or Los 'ANGELES, CALIFORNIA, ASSIGNO To THE ALLBRIGHT-I NELL COMPANY, A conronnzrioiv or ILLIN s.

raoonss FOR PRODUCING oArALYzEns-ron HYnnoeENATIoN.

that the following is afull, clear, and exact description of the same, reference being had to the accompanying drawings, and to the numerals of reference marked thereon, which form a" part of this specification.

his invention relates to an improved met 0d of producing finely p-ulverulent cat-alyzers, and more particularly finely pulverulent nickel catalyzers, adapted for use in the The invention is based upon the discovery that nickel, in bulk form, which possesses practically no catalytic activity, can be converted i to a finely pulve'rulent nickel catalyzer which is highly catalytic by subjecting the bulk nickel to a mechanical grinding or attrition or abrading operation in an ap-- paratus of the type commonly known as a tumbler or ball mill, or pebble mill. As a result of the' operation to which the bulk nickel is subjected, there is developed in the- "nickel a high degree of catalytic activity. which renders the resulting finely pulverulent catalyzer well adapted for use for various purposes, and particularly for use in the catalytic hydrogenation of unsaturated fatty bodies such as the unsaturated fatty acids and their glycerids or esters.

I have further ascertained that the treatment of the bulk nickel, and the conversion of the bulk nickel into an active catalyzer,

can be effected with-particular advantage, in an apparatus of the character referred to,

added use of a finely divided abrasive which is free from anti-catalytic properties, and which .will be present-at the end of the operation in intimate intermixture with the finely pulverulent nickel catalyzer cial to the development in the nickel of the desired catalytic properties. As such forms unsaturated oil, and the 1,331,904. Specification of Letters Patent.

' Application filed June 7, 191a. Scria1 No.- 238,655. 1

Patented Feb. 24, 1920. Y

of nickel may mentioned nick e1 shot, or I nickel in lump form, or turnings, clippings,

or other forms of nickel adapted and available for use for the production of an active nickel catalyzer. a

The invention will be further described and illustrated in connection with the accompanying drawing illustrative of one of the forms of apparatus adapted to the practice of the process of the present invention. In the accompanying drawing there is lllustrated in' longitudinal vertical section and with parts in elevation, a tumbleror pebble mill, 1, of circular or polygonal shape,

mounted ina frame 2, which is j ournaled 1n upright bearing standards 3 and capable of being rotated by a pulley extension of the frame. preferably grain nickel, is introduced into the tumbler through a suitable opening (not shown), or by the removal of one end of the tumbler as 5. Extending into one end of the drum, through one end of the bearing frame 2, is an inlet pipe 6, and extending mto the other end thereof in a similar manner is an inlet p ipe 7. "The ulk nickel, in any suitable form,

may be introduced-into the tumbler or pebble mill, either alone or together with a finealy divided abrasive. 'When no abrasive is us the nickel-slot or other form of bulk nickel will, during the rotation of the tumbler,be subjected to attrition or abrasionfand the bulk nickel will be gradually converted into finely divided nickel particles. This operation may be carried out at ordinary-tan peratures, and frequently, without extra precautions, although it is sometimes advantageous, and may even be desirable, to protect the nickel against oxidation during the operation. This may be effected by the introduction of a. non-oxidizinggas, such as hy-' drogen, through the-pipe 6, or by the .intro-.

duction of a protective liquid, such as oil, through the pipe 7; or bythe introduction .of both a protective gas and a"protective liquid. When the protective liquid is an hydrogen, some catalytic ydrogenation of the oil ma be brought about during the production o the catalyzer, and'particularly if the temperature is'raised to such a temperature as'will materially promote the catalytic hydrogenation process.

1protective gas isa secured upon an The bulk nickel,

When an abrasive is used, it may be added either in small amount or in large amount. When added in small amount, the mckel shot or other nickel particles will still be brought into abrasive relation with each other, and the abrasive action will be romoted by the intervening finely dlvided abrasive. When larger amounts of abrasive are used, the nickel shot orother nickel particlesmay be entirely-separated from each other'so'that' the action is essentially an ac tion of the abrasive upon the nickel part1- cles'. When an abrasive is used, a protective liquid; such as'oil, or a protective gas, such a as hydrogen, may be also employed in the manner above described.

' During the rotation of the tumbler or pebble mill, theb'ulk nickel will be subjected to a rubbing on grinding or abrasive action, with resulting attrition or grinding or abrasion' of the bulk nickel, and with accompanying development in the resulting finely divided nickel of a high degree of catalytic activity. The operatlon' is preferably carried on under such conditions and for such a time that the nickel will be brought into afinely pulverulent state readily adapted to be maintained in suspension in a liquid medium, as, for instance, in the fatty acid or its ester to be hydrogenated; but as the development of the catalyticall active condition of the material seems to I in part at least a function of the attrition incident to the operation it I is not absolutely necessary that the mater1al,

or all of the-material, should be brought into a finely pulverulent form. It may, in some instances, in part at least, have a different ph sical form than that 'of fine powder, provided always that-the operation has been carried on under such conditions and for such atime as to develop and maintain in the ultimate particles the desired catalytic 7 activity.

Where the nickel employed in bulk form is metallic nickel, the catalyzer roduced will similarly be .of a metallic c aracter, substantially free from oxygen and oxids which. are always present in catalyzers produced by the incomplete reduction with hydrogen of nickel oxid or similar reducible nickel compounds.

The abrasive, whenused, ispreferably of a finely pulverulent character. I have thus found abrasives of about 200 mesh as well adapted for use in the rocess of the present invention. The "fine y divided abrasive should be'free from anti-catalytic pro erties and fromconstituents prejudical to t e development of the desired catalytic activity.

Among the available abrasives may be mentioned silica, quartz, alundum, emery, car-:

borundum, etc.

ere'an abrasive is used, thefinely pulverulent l product resulting from the opera- .tion will contain the finel .divided abrasive in intimate admixture with the finely pulverulent catalyzer. This composite prod- .uct, containing the catalyzer particles and the abrasive, is available .for use, without separation of the abrasive," for catalytic purposes, inasmuch as' the'finely d vided abrasive will not usually be prejudiclal, and may even be advantageous in thecarrying out of the catalyticprocess.

Where a protective liquid, such present during the operation, there willresult at the end of the operatibn a more or less thick oil mud containing the finely divided abrasive and the finely divided. 7 catalyzer particles in suspension in the oil.

It will be'evident that varying amounts of oil can be used as well as varying amounts of abrasive, and that the resulting product will correspondingly vary in its oil and abrasiiecontent, and in. its content 0t. finely divided catalyzer particles. During the tumbling or pebble mill operation the minute particles of the nickel separated from the'bulk nickel will be enveloped by the oil' and maintained in suspension therein and carried thereby. These particles will also be thereby protected from contact with the air which may be present within the tumbler or pebble mill.

asoil, is

The amount of finely divided catalyzer uce an' exceedingly finely divided.

oils, for considerable periods of time and withbut slow settling out therefrom. The particles teiid to approach colloidal particles in finenessor size. Such a finely divided catalyzer is well adapted for use in the catal ic hydrogenation of oils and. can be readi y maintained in suspension therein.

In many cases the'finely divided abrasive will be of adifi'erent order of fineness from the finely divided catalyzer particles roduced, and will tend to settle out at a di erent rate. In such cases it is possible to effect a partial separation of the finely divided catalyzer and of the finely divided abrasive, forexample, by difierent-ial sedimentation, so that the catalyzer'may be.

available 'with a. less content of abrasive,

and so that the abrasive may be available, if desired, for further use in the production pf further amounts of finely divided catayzer.

In the operation of the tumbler or pebble the tumbler or pebble mill, can be varied,

as will be evident. So also, the charge of bulk nickel, which it will contain, will var with its size; and the amount of finely pu .verulent nickel catalyzer produced will also vary with the length of prolongation of the operation. When the operation has been continued a sufiicient time, with the resulting development and production of a sufficient amount of highly active pulverulent catalyzer, the operation can be stopped and the catalyzer withdrawn. Any remaining bulk nickel may be left in the apparatus for the next operation, and further amounts of bulk nickel may be added thereto together with further amounts of abrasive and protective liquids such as oil, etc. The operation can be then repeated in substantially the manner above described.

From the foregoing descrlption it will be evidentthat the process of the present invention is one of marked simpliclty, re-

quiring a minimum of attention and super-' vision. The started, may be allowed to continue without attention for long periods of time, un-

til-the operation has progressed sufliciently "to give the desired amount of catalyzer, in

the desired state of subdivision and catalytic activity. 7 e

As compared with the processes of the prior art involving the reduction of reducible nickel compounds with hydrogen at an elevated temperature, it will be noted that the present process enables the chemical methods of solution and precipitation,

for converting bulk nickel into a reducible nickelcompound, to be done away with; and also enables the furnace operation, for reducing the reducible nickel compound and producing the reduced nickel catalyzer, to

be done away with; and that the present process not only eliminates these elaborate and expensive chemical operations, but enables a finely divided catal zer, of hi h catalytic activity, to be pro uced direct y,

in metallic form, fromv the raw metallic nickel, possessing practically no catalytic activity.

The ;product produced according to the present invention is moreover distinguished from finely divided catalyzers roduced by reduction with y 't e evated tethball mill operation, 'once .a ball mill'oiperation in peratures of reducible nickelcompounds in that it is essentially metallic in character,

when produced from raw metallic nickel,

k and in that its particles, although they may be of microscopic size, are nevertheless characteristic of the mechanical operation b which they are produced.

When produced in the mud containing the catalyzer particles, either with or without the finely divided abrasive.

Having thus described my inventionwhat I claim is:

1. The method of roducing acatalyzer, which comprises su jecting substantially presence of oil,- the product will be a more or less thick non-catalytic catalyzer material to a combined rubbing, squeezing and percussive action, and thereby producing a finely pulverulent catalyzer of high catalytic activity. 2.. The method of producing a. catalyzer, which comprises subnectin catalyzer ma-' terial to' a ball mill operation in admixture with a finely-divided abrasive, and thereby producing a finel pulverulent catalyzer in admixture with t e abrasive.

.3. The method of producing a catalyzer,

which comprises subjecting the catalyzer material to a ball mill operation in the presence of a protective liquid and thereby producing a finel pulverulent catalyzer in suspension in said llquid.

4. The method of producing a catalyzer, which comprises subjecting catalyzer material, in admixture with a finely-divided abrasive and a protective liquid, to a ball mill operation, and thereby producing a finely pulverulent catalyzer in suspension in said liquid and in admixture with the finely ulverulent abrasive. 5. T e method of producing a catalyzer,

which comprises subjecting substantially non-catalytic bulk nickel to a ball mill o eration, and thereby producin a finely p'u verulent nickel catalyzer "of igh catalytic activit p v 6. e method 05 roducing a catalyzer, which comprises u jecting substantially non-catalytic nickel to a combined rubbing,

squeezing and percussive action, and thermal-5 by producing a finelly pulverulentnielgel a yt1 cat zer. of high c'ata c activity.

which comprises sub ectin bulk nickel to a ball. mill 0 eration in' admixture with a finely divide ducing a finely pulverulent nickel catalyzer in admixture with the abrasive.

8. The method of producing a catalyzer, which comprises sub ecting bulk nickel to protective liquid and thereby producing a finely pulverulent nickel catalyzer in sus pension in saidiliquid.

9. The method'iof producing a catalyzer,

presence of a 7. he method of producing aca aly i abrasive, and thereby pro-.

I which comprises subjecting bulk nickel, in

5 verulent nickel catalyzer in suspension in said liquid and in admixture with the finely I \pulverulent abrasive. FY 10. The method of producing a catalyzer, which comprises subjecting. the bulk nickel 0 to a ball mill operation in the'presence of a fatty oil. and thereby producing a finely pulverulent nickel catalyzer in suspension in said oil. v i

11. The method of producing a catalyzer,

which comprises subjecting bulk nickel, in 1:

nickel catalyzer in suspension 1n the oil and in admixture with the "finelyi pulverulent 20 abrasive. p

' In testimony whereof I have hereunto subscribed my name in the presence of two subscribing witnesses. f

BENJAMIN W. ELDER. Witnesses:

A. WIGHTMA'N,

F. N. CLAFLIN. 

